JPH03504099A - Heteropolycyclic compounds supported when decomposing and removing late transition metals - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Heteropolycyclic structure supported when separating and removing late transition metals The present invention is based on the periodic table. Regarding the heteropolycyclic compounds supported when separating and removing the latter transition metals shown Ru.

Background technology The inherent optical loss of glass compositions containing heavy metal fluorides is extremely high in the near and mid-infrared ranges. It's low. For this reason, the magazine “Light Wave Technology (1, igh)” by Tran et al. Twave Teehnologyll, Volume LT-2, Pages 55B-58 6 (1984), glass compositions containing heavy metal fluorides are exposed to high-energy infrared radiation. In the fields of laser transmission optics and ultra-long fiber optic links. It has high utility value. On the other hand, various impurities such as transition metal ions are kept at extremely low levels. Although pillion particles are usually present to some extent within these glass compositions, An equivalent amount of light is absorbed which is undesirable. Therefore, from these glass compositions, especially glass From the water-soluble and other compounds used as starting materials in making the lath composition, Conyl compound ion contaminants need to be removed.

Typical fluozirconates used in the optical field are zirconium and vanadium. It is a fluoride consisting of umium, barium, lanthanum, aluminum, and sodium. Ru. Hafnium fluoride replaces zirconium fluoride in the outer layer of the fiber. . Therefore, the starting materials containing Zr-Bas I-as^I, Na and )If are contaminated. It is necessary to purify dyed products, especially by removing transition metal ions. On the other hand, fluorozirconium Fibers composed of acid salt glass compositions may contain substitutes for one or more of the components listed above. In addition to this, Gd, Li, Pb, Th, Ca%Y, etc. It can also be made using other formulations containing metal fluorides. Zirconium is heavy Metal fluoride is present at high levels in glass compositions and is usually the primary treatment target. be done. A corresponding starting material is a water-soluble zirconyl compound, which It is purified as a liquid, and then zirconium is precipitated as a hydroxide or oxide. .

The most important transition metal contaminants in fluoride-containing glass compositions and precursors There are Co, Fe%Ni and Cu.

When using other various metal components, contamination such as Co, Fe, Ni and Cu For example, high purity lanthanum oxide has a high refractive index. They are used in optical glass manufacturing, and other rare earths are used in solid-state devices. solid state laser The presence of certain impurities at low levels can have significant adverse effects when It will be done. In these or other cases, ``a small amount of the above-mentioned contaminants may be present.'' However, undesirable effects occur and greatly affect optical, electronic and magnetic properties.

Generally, transition metals are divided into several groups. For example, B.F. - The Chemical Sosa, written by Johnson (B, l”, Q, Johnson) The Chemical 5ociety, London, 197 2. Volume 1 [Organic Chemistry of Transition Elements (InorI!!anicChemistry)] Titled y or the Transitior+Elements) J According to the book, these elements are the transition metals in the second half of the periodic table, and groups 3a and 48. The first half of the transition metals belonging to the scandium and titanium groups, respectively, are separated by column. The second and third transition series, which have weak reactivity and contain relatively large amounts of precious metals, and the One transition sequence can be divided into periods. For this reason, using the method of the present invention The contaminants to be removed are the latter half of the transition metals [groups 5a, 6a, 78 of the periodic table, Group 8, Group 1b, Group 2b (this nomenclature is in the 4th edition, Wiley Interscience) 1iley-1nterscience, New York, New York K., 1980, F. A. Cotton and G. - “Advanced Inorganic Chemistry (Adva)” by Wilkinson (G, filkinson) nced Inorganic ]. Many of these elements, especially those of the first successional series, are in the oxidized form. It exhibits strong absorption in the near-ultraviolet, visible, near-infrared, and mid-infrared regions. this Many of the oxidation states are paramagnetic.

Other methods of removing late transition metal contaminants include chemical precipitation (co-precipitation), fractional crystallization, distillation and sublimation. Many methods of separation from metal compounds are used. Among them, the most widely used, Large-scale, highly efficient methods for removing and purifying late transition metal impurities include solvent extraction and and ion exchange method.

J. Korkisch and A. Faradeh (＾, F. arag), Zeit schrirt ruer analysis chwie), ..., 81-88.1959 document "Strongly basic ion exchange amberlite (A Zirco as a negatively charged sulfate complex of IRA-400 ■ Analytical chemistry of enrichment and thorium, titanium, iron, aluminum, etc. According to ``Method of Separating It from Elements'', zirconium is 0. Amber from IN sulfuric acid solution - Light IRA-400 or Dowex 1 or 2 anion Because it is strongly retained by exchange resins, zirconium is compatible with copper, trivalent iron, cobalt, and nickel. It can be separated from many elements including Kel. Zirconium then contains 4N hydrochloric acid eluted from the bed. F double knee stake (F, W, E, Analytical Chemistry (Analytical Ch. esigtry), 31.1974-1977.1959 Dilution from titanium, ferric, aluminum and other cations by matography According to the ``Ruconium Separation Method,'' BioRod was extracted from 2N hydrochloric acid solution. AG501. By sorbing zirconium on the X8 cation exchange resin, 2 Separates zirconium from many elements such as valent and trivalent iron, copper, nickel and cobalt. A separation method was adopted. At this time, zirconium is eluted with a 5N hydrochloric acid solution.

These ion exchange methods generally have various drawbacks. Zirconium is an impurity is pre-sorbed into the ion exchange bed, thus improving both the efficiency and capacity of the bed. Is zirconium in zirconium solution limited? If 1IIf is moderately high , elution must occur whenever a small amount of zirconium solution passes through the bed. No. The capacity of cation exchange resin is usually less than Smez/laQ, and anion Since the capacity of the exchange resin is 2teg/m (or less), the IM Z with a capacity of 1.25 or less 1 volume of cation exchange resin (91g#! or 5teg#! of Zr) Also, less than 0.5 volumes of IM Zr solution is sorbed to 1 volume of anion exchange resin. Sorpted. Furthermore, in any case, the eluted Zr solution is highly acidic and contains zirconia. Since a large amount of base is required to precipitate aluminum hydroxide (hydrous oxide), the capacity is will increase significantly, increasing the risk of recontamination. Therefore, from zirconium solution to late stage It is highly desirable to preferentially sorb migratory metal impurities onto ion exchange or sorption media. therefore, the affinity of the medium for these impurities is reduced by its affinity for zirconium. It needs to be higher than gender. For conventional cation exchange resins, Zr or similar ions of elements such as If.

La and AI ions generally have a high charge density (ratio of charge to size), so Ions of late transition metals such as Fe, Co, Ni, and Cu are more likely to be sorbed to the resin. water. In the case of this well-known anion exchanger, the sorption degree of various metals is determined by each anion complex. depends on stability and charge density. For example, if the concentration of chloride is high, A. Marinsky (J, A, Marinsky), Marcel Detska (M. Arcel Dekker), published in New York in 1966, “Aeon R.M. Diamo in Chapter 8 of the literature titled "Exchange", pages 277-351. (R, L Dia■and) and D.C. Whiteni (D, C.

According to the article "Resin Dilution Selectivity for Condensed Ice Aqueous Solutions" by Ihltney), Co, Cu, and Ni are relatively less present in anion exchange resin than Zrs, Hr, and Ga. It is sorbed without being sorbed. According to the same document, C01ll+ and Cu are obtained from nitrate medium. It is not adsorbed by anion exchangers. Therefore, the well-known conventional anion exchange resin is Z The late transition of solutes from solutions containing large amounts of other solute metals such as r, 11r and Ga It is not considered useful in removing transferred metals.

Purification is required to reduce the content in fields such as optics and electronics, and the most important species , e.g. Zr-, Hf5I, a, Ill+ or other polyvalent metals have very low base metals. It is stable in solutions with a Beha value of 2-3 or less. For this reason, cation exchange or bovine rate ion exchange resin, e.g. Beha value reduced from about 4 to less than 2 Bio-Rad Lavatory's Killex ( This by BioRad Laboratories Chelex) 100 This prevents the purification of elements.

Klein et al., Volume 24, Page 517, 1985, “According to Optical Engineering, standard Iron, cobalt, nickel and copper are extracted from zirconyl ion solution using on-exchange properties. It can be removed. On the other hand, the column capacity is not given and is extremely low based on the above literature. Zirconium ion parent for both cation and anion exchange resins It can be considered that there is a high level of compatibility. In the case of Fe%Co and Ni, the residue after ion exchange The distillate concentration is 0.38ppm, 0.36ppm and t, tspp*, or each flow 5%, 5% and 16% of the initial level of input fluid.

Therefore, the selection of ion exchange media, i.e. ionic bone collection media, against late transition metal impurities. It is strongly desired that the charge density be high in the presence of relatively high concentrations of ions. Ru. This selective sorption tends to concentrate trace impurities in the solid medium. can be analyzed after.

Late transition metal ions that can be used in solvent extraction methods to separate these ions from aqueous solutions Various organic compounds that form complexes with are known.

The following structure NC, H, -C,)1. Bipyridine or bipyridyl with N The main component of the heteropolycyclic compound is certain late transition metal ions, especially ferrous iron. It is known that copper ions form colored complexes with copper ions.

Generally, a heteropolycyclic compound has two aqueous rings that do not directly melt into each other; At least one of the rings contains - or more heteroatoms, especially nitrogen atoms. is defined as a compound that Gee Huderete, both in Columbus, Ohio. Ick Smith Chemical Company (G, Frederick Sm1th Published by Chemical Company and published by H, Di co-authored by G.F. Smith (G.F. Sm1th), 1960. According to the literature entitled "Ionic Reagents" and the second edition of 1972 "Copper Reagents", the structure N C5)1. - Many compounds containing C, 114N form complexes with the ions mentioned above. do. These compounds have the following structures: 1. IO-phenanthroline and its dielectric , for example 4,7-diphenyl-1,10-phenanthroline (basophenanthroline) Phosphorus (bathophenanthroline), 2,9-diphenyl-1 , 10-phenanthroline (neotabroin), 2,9-diphenyl-4,7- Diphenyl-1,10-phenanthroline (backproine) and 2,2°-biproine Contains quinoline or 2,2'-biquinolyl (cuproine).

Other heteropolycyclic compounds that form similar complexes have structures such as bipyridine or phenyl They are not directly based on the troline structure and contain two unfused rings, at least One ring also contains a nitrogen atom. This compound contains 2,4,6-1-riviridine. (TPTZ) and hiscine-phenyl-2-pyridylketoxime.

According to U.S. Pat. No. 3.095.382 to Hach, The iron contained is approximately 40% NatStOt, 60% NaHSOl or Nayst. ost 1.4% mixture of heterocyclic compounds such as 10-phenanthroline Determined by colorimetric method. Approximately 0.1% of the mixture is added to 25a & The oxides are dissolved, the iron is reduced, and the sample becomes loose with a Beha value of 6.5. be attacked.

The formulation of the mixture can vary over a wide range.

H Gel ()1. Diehl) and G.F. Smith (G.F.

Co-authored by Ss i t h) in the above-mentioned literature entitled “Ionic Reagents” and “Copper Reagents” According to alcohol or 3-methylbutan-1-ol, ]-hexagonal and nitrobene Extractable into solvents such as zene. On the other hand, solid absorbent or ion exchange medium The use of biomass has many advantages over solvent extraction methods in removing trace impurities.

Particularly when packed columns or beds are used, theoretical plates can be Many Hei 1 (equal 1hrat 1on) called ical plRte) A separation stage is required. Liquid phase miscibility, impurity concentration at the interface, and contamination of the production stream by solvents. The problems of contamination, and the presence of hazardous solvent vapors are avoided.

Furthermore, H.G. (B, Diehl) and G.F. Smith (G., F. According to the above-mentioned literature entitled "Ionic Reagents" and "Copper Reagents" co-authored by J.D., Sm1th) If so, heteropolycyclic compounds that form complexes with late transition metal ions are usually It is particularly effective only for one or more of the ons. For example, bipyridine and fena Compounds with a substituent on the carbon atom adjacent to the nitrogen atom in the ring of the throline structure are copper. It forms a colored complex with iron, but not with iron. Therefore, traditional solvent extraction methods , different complexing compounds are used for different ions. For example, 1 for iron ．． 10-phenanthroline, bathophenandroline, TPTZ and phenyl-2 - Pyridyl ketoxime, and for copper, cubroin, neotabroin and bantam. Cuproin is used.

According to U.S. Pat. No. 3.886.080 by Hueker et al. , 1.10-7 enanthroline (0-phenanthroline) or neotabloi various organic chelating agents, including heteropolycyclic compounds such as Other killers like Norin (Oxin), Sinacin and Salicyraldo Cow Sim The agent can bind silica, silica gel, glass, porous glass, etc. using an intermediate silane binder. Insolubles like bentonite, hydroxyapatite, alumina and nickel Can be combined with Inorganic Tei Yariya. According to this U.S. patent, the chelating agent is an azo bond The silane binder is combined with the silane binder by the agent. The immobilized chelating agent removes Fe from solution, Used to remove trace metals such as Cu%no, Zr, V, 1 and Ti It is possible. On the other hand, silanization is a complex and expensive technique, but it is When used to remove trace amounts of metals from raw materials used in other fields, It is undesirable to be contaminated with a large amount of Si. The expected filling of the chelating agent into the supporting body is low. In order to obtain the removal efficiency of various metals when using a porous glass oxine composition, In experimental examples, it was observed that zirconium was effectively sorbed, and this mixture The material is suitable for selectively separating late transition metal impurities from zirconium solutions. It shows that there is no. By Plueddenar+++ According to U.S. Patent No. 4.421.654 and U.S. Patent No. 4.448°694 , an inorganic solid such as silica gel treated with a silylating agent that is a polyamine dielectric Transition metal ions are dissolved by a method that brings the substrate into contact with a solution containing these ions. It can be removed from the liquid. This method mainly uses bipyridyl and phenanthroline structures. Do not use a board that is used as a body.

British Patent No. 1.355.535 describes how metal ions can be removed from a solution containing the metal ions to be removed. A method for extracting metals is shown in which stable complexes can be formed with the metals. peat or lignite or lignite char in the presence of ammonia Contacting the adsorbent with the solution. Ammonia derivatives are aliphatic amines, hydroxy - Aliphatic amines or nitrogen-containing heterocyclic compounds such as pyridine. one On the other hand, this patent does not explain heteropolycyclic compounds. This method is Used when recovering metal valuables from solutions. This patent also states that, for example, Zr , TdL^1. Late transition metals from solutions containing La or other polyvalent metal ions For information on how to selectively remove or separate various metals, such as removing ions, Not mentioned. Furthermore, the major difference between this prior patent and the claimed invention is that this prior patent According to the patent, ammonia derivatives cannot be used when pretreating carbonaceous substrates and added to the genus solution. This method is used in the present application when removing contaminants from effluent from a nuclear factory. This is less suitable than the case of using a pretreated support as in the invention.

U.S. Patent No. 4.222.892 by Motoshima et al. , to create charcoal impregnated with oxine (8-hydroxyquinoline) A method is shown in which the charcoal is treated with solid oxine until it is impregnated with oxine. It is brought into contact with charcoal. This patent includes methods for removing heavy metals from solutions. In most cases, supported oxins are used, but the selectivity also depends on non-oxins. The supported reagents are also not described.

U.S. Pat. No. 4,659,512 to Macedo et al. using silicate glass, silica gel or charcoal containing alkylene amines. A method for removing metal species from solutions is described. On the other hand, heteropolycyclic compounds is not used.

According to U.S. Patent No. 3.917.453 by MNligan et al. , 1.10- Phenanthroline or 4,7-diphenyl-1,]0-phenanthroline is applied. However, this patent does not include removing late transition metal ions from solution. There is no explanation for the separation or separation from other ions.

In addition to removing dissolved late transition metals from solution, e.g. and the last two rows of group 8 noble metals. It is often desirable to separate them from each other.

Besides the problem of removing dissolved late transition metals from solution, radioactive or toxic Management of metal species (e.g. Co-60, Co-58 or Fe-59), precious metals For purposes such as recovery of metals (e.g. pt and Pd) or analysis of trace metals, It is often necessary to fix and concentrate metals from various media.

Disclosure of invention One object of the present invention is to provide a method for efficiently removing late transition metal species from a fluid. It's about doing.

Another object of the present invention is Zr5Hf, I, 1, AI, Ga, In, Sc, Y and Fe in the presence of large amounts of other dissolved metal species such as Ba and Ba.

Selective removal of dissolved late transition metal species such as Co, Fli and Cu from the fluid The goal is to create an absorbent medium that removes the

Another object of the present invention is to provide a method for removing dissolved late transition metals from acidic solutions. It's about doing.

A further object of the invention is to provide highly transparent optical glasses or optical fibers, especially Extremely pure starting material for the creation of fluozirconate glasses and fibers The goal is to share ways to create a fee.

Yet another object of the present invention is to obtain a specific second half dissolved from a fluid containing two or more transition metals. An object of the present invention is to provide a method for selectively recovering transition metals.

late transition gold for management of radioactive and toxic species, recovery of precious metals, and analysis of trace metals. To provide an absorbent or ion exchange composition that concentrates the genus to a certain level. be.

According to the invention, a heteropolycyclic compound or a functional group is attached to a support. A composition is used which is fixed by Species of heteropolycyclic compounds are chemical or can be attached to a solid support by physical sorption. The solid support is porous. The activated carbonaceous material preferably comprises charcoal.

When the heteropolycyclic compound used in the present invention is in solution, the dissolved F es Forms complexes with late transition metals such as Co, Ni and Cu. present invention According to an important embodiment of the present invention, the heteropolycyclic species is disposed on a solid support, in particular a support. Heteropolycyclic species are dissolved even when sorbed to the inner surface of the porous structure of the body material. It has a remarkable affinity for late-transition metal species, i.e., complex-forming ability. heteropolycyclic When a compound species is loaded onto a support, the heteropolycyclic compound species attached to the support The removal capacity of late transition metal species dissolved from solution is sufficient to Become big. Reaction kinetics between metal species and supported heteropolycyclic compounds containing functional groups When this solution passes through a bed or column (tower) filled with medium, the solution A large amount of metal species can be removed from

The heteropolycyclic compounds used in the present invention are not bonded via a covalent bond by a linking agent. It is attached to the solid support through sorption or precipitation. The preferred method is heteropolycyclization This method involves sorption from a solution of the compound. Also make sure the solution is not overly saturated. Optimal. It is worth noting that the medium obtained with high acidity and high salt content that the heteropolycyclic compound is not rapidly extracted from the substrate even after treatment with a solution of There was found. And the beds made of this medium are markedly It is useful for extremely efficient removal of late transition metal ions from large volumes of solutions. It turned out that.

The medium of the invention consisting of a heteropolycyclic species attached to a solid support is dissolved from solution. It is characterized by being able to remove late transition metal species extremely selectively. Importance of the invention According to a specific embodiment, the selectivity of this medium is such that late transition metal species are from bedding per million to less than 1 part per pillion for the concentration of other metal species in range) Even when present in solution, unlike general ion exchange resins, Zr'', Hr Other dissolved metal ions such as ``, l, a'' and ^ls° The selectivity for late transition metal species is higher than the selectivity for metal species.

According to another important embodiment of the invention, a heteropolycyclic compound attached to a solid support Even when the pH value is extremely low, the medium consisting of compound species can be Transfer metal species can be effectively and selectively removed. Richmond, California Bio-Rad Laboratories (Bio-Rad l, aborato) [Chelex 100 kire] from July 1978 Bio-Rad Laboratories product information titled ``Separation of Metals Using Extract Resins'' According to 2020, iminodiacetate styrene-divinylbenzene copolymer Rio-Rad Chelex 100 The capacity of the above-mentioned chelate ion exchange media, such as When the P/% value is in the range of 4 to 2, it decreases rapidly, and when the P/% value is less than 2, it is extremely low. Become. On the other hand, 10 ta (1 g of 1, 1 O-phenanyl per 1 charcoal) The capacity of the troline-treated charcoal column (tower) is approximately IO% of Zr0t. Pe, Co, It was found that the removal of Ni and Cu was quite large.

According to the present invention, in addition to removing late transition metal species from a solution without discrimination, the solid support A heteropolycyclic compound is immobilized on a support, and late transition metal species are selectively separated from each other. For example, even if the acidity of the solution is extremely high, Pt can be removed from a solution containing Rh or Ru. Alternatively, a separation medium and a separation method for selectively removing Pd are provided.

According to the present invention, in order to purify this solution, late transition metal species are removed from the solution, and In addition to separating the late transition metal species from each other, the heteropolycyclic compounds are also separated on a solid support. Compositions that fix and concentrate late transition metals that are present at low levels in solution. law is provided. The composition or concentration method may include, for example, radioactive or hazardous It can be used for waste management, municipal resource recovery, and analysis.

BEST MODE FOR CARRYING OUT THE INVENTION To remove dissolved late transition metal species from fluids containing late transition metal species, The fluid is passed through a composition of porous supports comprising pores connected to the porous substrate.

The characteristics of this composition make it stable with - or later - F late transition metal species. one or more heteropolycyclic compound components capable of forming complexes or compounds with is included. The heteropolycyclic compound component includes a heteropolycyclic compound component. It effectively complexes with the dissolved late transition metal species and reacts with the composition of the porous support. The dissolved late transition metal species are present in the amount necessary to react or adhere to the (b) Forms a complex or compound with the polycyclic compound component and is removed from the solution.

As mentioned above, the heteropolycyclic compound components include at least a few components that are not directly fused with each other. both have two rings and one or more heteroatoms, especially a nitrogen atom as part of the ring. and at least one ring having. In particular, the heteropolycyclic compound component of the present invention has at least one pyridinoid ring, i.e. substitutes one of -CH-1 in the ring An aromatic ring consisting of 6 -CH- members having a nitrogen atom is included. The advantages according to the present invention Preferred heteropolycyclic components preferably have a 2,2” position as shown below. Included are bipyridine or bipyridyl structures with a nitrogen atom.

Various substituents can be attached to this structure. For example, if another ring is present in the bipyridyl structure, Indirectly or directly bonded or fused to the bipyridyl ring. Most preferred of the invention The new heteropolycyclic compound component has nitrogen atoms at the 1 and 10 positions as shown. Contains a phenanthroline structure.

Various substituents can be attached to this structure. Specifically creating a sorption medium according to the invention Case 1. ] O-phenanthroline itself was found to be effective. heteropolycyclic When a compound component is sorbed onto the surface of a support, 1.10-phenanthroline itself or or its salts, for example 1. In ~ Phenanthroline hydrochloride is used used. For example, G.F.D., both located in Columbus, Ohio, Miss Chemical Company (G, Frederick Sm1th Che+1 ical Company) and published by H, Diehl. and G.F. Smith (G, F, 5w1th) co-author, 1960 “Ion” According to the literature entitled "Copper Reagent" and the second edition of 1972, "Copper Reagent", the late transition metal Heteropolycyclic compounds that form complexes with ions usually contain one or more of these ions. It is particularly effective only against For example, bipyridyl or phenanthroline structures Compounds with substituents on the ring nitrogen atom and the adjacent carbon atom form colored complexes with copper. However, it does not form colored complexes with iron. Compounds without this substituent are resistant to iron. It is preferable for copper, but it is not preferable for copper. For example, according to this literature, Lysyl and phenanthroline compounds and their derivatives contain cobalt and nickel. Not among the usual reagents used to form complexes. According to the teachings of these documents: It is worth noting that these various late transition metal ion mixtures contain many other metals. Even when present in solutions containing ions, many such as Fe, CO1Ni and Cu It was found to be effective in removing late transition metal ions from solutions. paraphrase In particular, the selectivity of 1,10-phenanthroline-supported media is Selectivity for late transition metal ions as a group rather than selectivity for individual metal ions The selectivity for metal ions is more pronounced. The present invention includes Panfena. Other phenanthrolynes such as antroline, neotabloin and bancproin derivatives, bipyridyl derivatives such as tabloin, and TPTZ and non-phenylene derivatives. Other heteropolycyclic compounds such as -2-pyridylketoxime can also be used. .

The pores of the porous support are interconnected. The porous support of the present invention mainly has internal porosity. is an activated carbonaceous material made of amorphous non-graphite and carbon with a high surface area. be. This material includes activated, coke, and anthracite. cite), char, lignite, e.g. lignite or bituminous coe, lignite char, and and charcoal. carried out by live gas or chemical treatment of carbonaceous materials; Large surface area or large porosity is provided. Charcoal as a support is preferred.

Charcoal is a form of amorphous carbon that can be mixed with wood, sugar, coal and other charcoals. obtained by decomposition distillation of quality materials. More specifically, activated carbon The material has a large surface area, making it capable of absorbing gaseous and liquid states. activated The specific surface area of the carbonaceous material ranges from about 10 to about 5000 m"/g, preferably about 20 m"/g. 0 to about 3000 m"/g. The pore diameter ranges from about 0.5 to about 10000 m"/g. It is surrounded. Activated granular or powdered carbonaceous materials have a porous structure; This is achieved by expelling components from the carbonaceous feedstock and partially oxidizing the residue.

Oxidation is usually carried out with steam, flue gas, air or carbon dioxide. used in the present invention The charfur used is optimally obtained from other nut grains such as coconut. Ru.

The activated charcoal can be simply contacted with a solution containing the heteropolycyclic compound. It has recently been found that this method is effective in sorbing heteropolycyclic molecules. sorption The process is fast and the sorbed molecules are strongly attached to the charcoal but not very rapidly ( These molecules are reactive towards late transition metal ions, and the sorbed The amount of heteropolycyclic compound requires a considerable volume in removing this metal ion from solution. It is a sufficient amount to give a quantity. The solution containing the heteropolycyclic compound is preferably a solution shake or stir the solid content to bring it into contact with the solid support in the container, or They are passed through pillars filled with bodies. Also, pH value change, solvent exchange or Precipitation methods such as solvent evaporation can be used. For example, 1. IO-Fenanthro Phosphorus is much less soluble in water than its hydrochloride salt, so it increases the pH value. It can be precipitated from hydrochloride solutions. For example, U.S. Pat. ．． 222.892, solid or gaseous phases of organic compounds. Sorption of these substances is also possible. It is preferable to adopt a sorption method from solution, in which case A heteropolycyclic compound component is attached to the support. This method is based on the Shu Covalent bonding as shown in U.S. Pat. It is less complicated and costs much less than the conventional method. Sorption method introduces silane When loading high levels of heteropolycyclic compounds into the substrate, there is no need to Adoptable. It is worth noting that even if sorption is replaced by a covalent bond, the heteropolycyclic The formula compound is not excessively leaked or released, and this leakage traditionally Fe, Cu, Ni, and Co can be removed from Zr solution, and can be collected in charcoal. Separating the components of an acidic noble metal solution using 1,10-phenanthroline It could not be used in such fields (described in detail below). Also worth noting For leakage, use a highly acidic medium, such as 0.1M) ICI, approximately 0.5-1 pages. 10-20% Zr0C] in a medium with extremely high ionic power such as a solution. It's also small. To further reduce this leakage amount, untreated bearings, e.g. A second bed can be placed downstream of the treated bed.

The particle size of the solid particles ranges from about 0.5 microns to about 6000 microns. Like According to a new embodiment, a solution-supported heteropolycycle containing a dissolved late transition metal is passed through a column filled with formula compound components. The particle size of the solid particles in the pillars is approximately 25 microns. It is preferably in the range of - about 2000 microns. Heteropolycyclic support The loading of compound components ranges from about 0.01 to about 2000% dry weight, preferably about 0.1%. - in the range of about 50% dry weight, optimally in the range of about 1 to about 40% dry weight.

The substrate on which the heteropolycyclic compound is sorbed or attached is a fluid containing late transition metal species. be contacted. Preferably, this contact occurs within the filled columns. to be purified The solution contains a very high concentration of other metal ions, e.g. an equivalent concentration of 20% ZrO. 250g # of zirconium oxychloride or in water! LaUos ) s・61 (, solutions containing O. High concentration in the solution, usual) Og/ Dissolved metals present above C include alkali metals such as Ha, especially polyvalent metals. is included. The media described herein are of near-neutral or moderate acidity (below). Fluid with pH value 4.0 = 2°0) or highly acidic fluid (pH value 2.0-0.5) It was found that late transition metals can be effectively removed even from fluids.

In addition, when the solute concentration is extremely high and the acidity is high (solute is Z　rOc■2, equivalent concentration Even if the Zr0p degree is 20% and the Beha value is 0.5), one bulky Charcoal treated with compound media, e.g. I, 10-7 enanthroline More than 90% of the species Fe, Co, lli and Cu contained in a solution with a volume of O or more It was also observed that it was removable. The term "column volume (CV)" as used herein J means 1 volume of solution per 1 volume of charcoal or other substrate. child The performance of charcoal treated with heteropolycyclic compounds under conditions of bodies and ion exchange media, such as cation exchange media based on polystyrene, Anion exchange media, such as triethylenetetraamine or 8-hydroxyquinoline Charcoal, porous silicate glass, silica treated with other chelating agents heteropolycyclic compounds through sorption or covalent bonding with silanizing agents. The performance was found to be significantly superior to that of treated alumina.

A support on which a heteropolycyclic compound is sorbed, e.g. 1,10-phenanthroline. The treated charcoal contains chloride and oxychloride as the main anion species. , effective in removing late transition metals from solutions containing nitrates and acetates. Something was observed.

The solution containing the late transition metal to be removed is hydroxylamine hydrochloride. The oxides of species such as ferric ions or copper ions are treated with reducing solutes such as It can be converted into reduced products of species such as ferrous ions and copper ions. This is for example Can be used to stabilize solutions that come into contact with treated substrates and prevent colloid formation. be. Additionally, metal ions are removed from the colloidal material before using the treated support as described above. Microfiltration or ultrafiltration, centrifugation and recrystallization can also be employed to achieve this.

According to one embodiment of the invention, to remove dissolved late transition metals from solution, The solution is passed through a support bed or column containing the heteropolycyclic compound component.

This method is particularly useful in purifying solutions containing other metals in high concentrations. Highly charged is generally a major factor in improving the ability of ion exchange media to remove ions from solutions. Therefore, this method is particularly suitable for alkaline earth metals or group 33 and 4a of the periodic table. When other metals such as Group 3b, Group 4b and Group 5b metals are polyvalent It is most useful when the value of the other metal is 2 or more. Then of this solution Purified main solutes, such as Zr, Hr, Ti, Th, La.

AI, Ga, In5Sc, Y and Ba compounds are recovered in solid state with low loss Loss of optical glasses, optical fibers, homogeneous lasers, high-performance electronic devices, especially semiconductor devices. It can be used to create high purity products such as Concentrations of these other metals in solution The degree is high, usually l.

g/Q or more.

Beds or columns filled with heteropolycyclic components are dissolved late transition metals can be used to separate them from each other. For example, extremely highly acidic precious metal mixed solutions. If the liquid is subjected to a catalyst recovery method, the i,+o-phenanthroline treated char It is possible to selectively collect PT or Pd in the column consisting of coal, while Rh or Otherwise, Ru is not removed. Next, pt or Pd is under relatively large scale conditions. , filled with solutes, for example using concentrated acids or by chemical oxidation or incineration of the column material. It can be removed from the pillar.

The substrate containing the heteropolycyclic compound component also has low levels of transients present in solution. It can be used to fix and concentrate transfer metals. For example, Fe-59, Co-58 and toxic or radioactive species such as Co-60 in water streams, especially in high concentrations of other solutes. can be removed from a water stream containing water and fixed to a treated scaffold. pt or Pd Precious metals such as It is possible to concentrate the target metal from a solution containing a low concentration. Concentration can also be used for trace analysis It is effective for the following purposes. For example, water streams, especially those containing high levels of unmeasurable metals. Radiation contained in low levels such as Fe-59, Co-58 and Co-60 from To determine the level of sexual ions, contact the treated substrate with the solution and - Radioactive species are counted and then radioactive ions are removed by a suitable stripping process. can be concentrated in advance. Similarly, the management of radioactive or toxic species and precious metal recycling During harvesting, the sorbed species can be used using methods such as elution or incineration. Can be removed from the pillar. Alternatively, the pillar may be used to dispose of particularly toxic or radioactive waste. In this case, it is finally fixed and solidified. Dissolves low levels of late transition metal ions For these ions, the capacity of the processing substrate is small to effectively concentrate them from the solution. Both should have a bulk of about 10, preferably at least about 50. In other words, The concentration of these ions on the substrate is determined by the concentration of ions in the solution before it is contacted with the treated substrate. at least about 10 times higher, preferably at least about 50 times higher than the concentration.

Although the present invention will be explained along with the following experimental examples, the present invention is not limited to this specific experimental example. Not possible.

Experimental example 1 When removing late transition metal ions from solutions containing other polyvalent metal ions, the release A series of pillar tests were conducted using radioactive tracers. C-o-fe on - of test column material Phen, which contains 100 g of 1.10 in 16661 deionized water. - A solution containing phenanthroline monohydrochloride was added to coconut grains (-50 +100 mesh) along with 500 sff of activated carbonaceous material as the main component. It was made by stirring for 5 hours. The second test column had G-o-fen. 15g of 1,10-phenanthroline monohydride in 300ml of water Contains lochloride monohydrate (-monohydrate) 150 se silica gel (-35 + 70 The mesh was prepared by frontage ringing for 16 hours at a speed of about 60 rpm. Third For the test column material, analytical grade CGC-24 was used. A cation exchange resin known as 0 is used, which has an 8% cross-linked ion ll blade-1 00+ 200 mesh strongly acidic sulfonated polystyrene resin in New Jersey The Tea Bar in Philipsburg (Ph. 1ipsburg) Power Chemical (J, T, Baker Che*jcal) was adopted.

The fourth test pillar material was Dowcx for analysis (registered trademark>2-18). An anion exchange resin known as Tsushiyu's strongly basic quaternary amine polystyrene resin is combined with New Jersey's fillet. G.T. Bar Power Chemical Co., Ltd. located in Bussburg. 5th Te A cow known as Chelex (registration part 1) +00 for analysis is used for the pillar material. A rate resin is used, which has an iminodia of -200+200 meshes with ion Na. Cetate polystyrene (Bio-Rad, Richmond, California) ・We adopted Bio-Rad Laboratories.

The sixth test post was oxine-impregnated charcoal or C-oxine. , which is described in U.S. Pat. No. 4.222. by Motojima et al. Exactly as disclosed in Publication No. 892, 100 g of coconut was added to the 1000@Q flask. Add activated charcoal from Tutu grains to 500 se of water and 10 g of suxin crystals. It was created by shaking it with powder. The seventh test column material was porous silicate. l,10-phenanthrolyne covalently bonded to glass or GS-o-phene 3.886, by 5hucker et al. ．． In the above Experimental Example 4, 10 g of porous silica Togarasu was treated with 100@l of 10% (v/v) aminopropyltriethoxysilane. Reflux, wash the product with toluene, add 100 g of chloroform and 5 g of 18 in a mixture of triethylamine and 1 g of p-nitropenzeol chloride. Created by opening the ring for an hour, washing with chloroform, and finally air drying. It was. This product contains 300 mg of sodium dithionite in 100 mQ of water. Boil for 30 minutes, diazotize in cold 2MI'IC1 for 30 minutes, wash with cold water, 0g + & O, I M Mate 03 inner Te 200g of 1.10-phenanthro React with phosphorus for 24 hours at 0-6°C, wash with NaNOs solution, and HC I, diluted with distilled water and acetone and dried.

Each test column had a 5*t - of the material was used. Each test solution used in this test was 15.6% (w/w) ZeOCly, 16.3% b/w) BfOC in water Lt, and those containing 2.9% ^L(110,)s-9H,O based on water And so. Each solution contains 1 nCi/rw (l of Co-60 and 1 nCi/-f f Fe-59 was added. These solutions were forced through the column. This flow rate is In all cases, the average speed was 12m+2/hr. Collect samples of effluent at predetermined times These measured activities are compared with those of the influent to determine the contaminant removal. The dissolution factor (DF), the ratio of the influent activity to the effluent activity, was obtained.

CGC-240C-Oxine Co-Phen CV DF CV DF DF7 1.3 3 1.9 16 118.117 1.0 10 1.3 37 65.7G-o-phen GS-o-phe 5G 20. QCV DF DF 64 12.12 34.5 2 2.0 74 9.66 1.8 7 0.9 97 8.613 1.2 2 63 9.1F sea urchin 7ri 1 2-X8 4117 ri1 100 372 9.4CV DF 402 CV CV DF 402 8 J3 2.4 3 6.7 418 6.38 1.4 10 1.3 480 5.9516 4, 7 1’l　fOc　l　2 CGC-240C-o-7 engineering CM DF DF CV DF2 1.8 1.8 I+ 164.730 2, 9 35 2, 4 53 2, 0 66 1, 8 93 1, 8 103 1.8 AI (NOs)3 CGC-240C-o-phen CV DF DF DF20 258.0 32 4G0.589 173.7 75 48.8100 0.2 0.2 129 38.3109 0.9 150 42.2+82 43.9 224 41.1 25G 41.9 291 39.6 304 +4.7 318 1, 6 The measured activity is the combined activity of Co-60 and Fe-59.

Table 1 above shows the DF measurement results as a function of the volume passed through each building at the time of sampling. It was shown to. This volume is obtained by dividing the volume of the solution passed through the column by the volume of the column. It is expressed by the column volume number CV.

Removal of late transition metal ions from solutions containing other metals such as Zr, Hr and A1 1,10-7 enanthroline is sorbed onto the activated carbonaceous material. Its treatment capacity is the capacity of 1,10-phenanthroline of silica gel or The capacity is significantly higher than that of cation exchange resins, which are acidic and contain polystyrene. It became.

Experimental example 2 Using well-known chemical analysis methods, i.e. absorption spectrophotometry or plasma spectroscopy. A series of pillar tests are employed to extract late transition metal ions from solutions containing barium ions. This was done regarding the case of removing . The test material was C-o as explained in Experimental Example 1 above. -phen and Go-phen. In addition, Dovex (Dovex: registration) Trademark) was also tested, which was -20 + 50 mesh on ion CI, strong base Our company in Philbsburg, New Jersey, produces anion exchange resins for chemical analysis. A.T. Neuker Chemical (J.T.Baker Chemical) ) manufactured by ).

The pillars filled with each of the above materials of 5@Q are Tests were conducted in connection with the removal of on. These solutions undergo several late transitions. 1. Doped with one or more of the transfer metal ions. S.

This doping level for each ion was 2 mg/(!). It was forced to move downstream. In either case, the flow rate is 1 or about 10 mff/hr. did. The outflow liquid and inflow liquid to the column are absorbed as explained in accordance with Experimental Example 1. The analysis was performed using photophotometry or plasma spectrometry. Pass based on this result The resulting effluent concentration was measured as a function of column volume number CV. to the prescribed doping agent The treatment capacity of the column is the doping agent concentration in the effluent is the doping agent concentration in the influent. , that is, the removal of contaminants from the column with respect to the doping agent becomes less than a factor of 2. Calculated from the number of column volumes at time. The column test results for each main aqueous solution are shown in Table 2 below. show.

Table 2 Test solution Column medium Processing volume M (CV) Cu Fe Co Ni4.62%Ha(NOs)t Co-Phen >3 73 >373 83 >3730-o-phen <2 <2> <2> <2F Sea Urchin 7ri 22-X8 1 According to this result, Bariu When removing late transition metal ions from solutions containing aluminum salts, they are sorbed to charcoal. 1. The processing capacity of 10-phenanthroline was significantly different from other test materials. It became big.

Experimental example 3 Two types of solutions A and B containing noble metals were created using standard solutions. 0.1 for solution A 4M) Contain 20 mg/ρ of Pt, Pd, and Rh in IcI, while Solution B contains mg/Q of each of Pt, Pd, and Rh in 0.18 M) IcI. Included. Co-o-phen is 100 * (1 g of 1,1 in 1 of absolute ethanol) 10 g of activated carbonaceous material (previously (see experimental example) by frontage-ring treatment for 1 hour at a speed of about 60 rpm. Created by Each solution was placed in a borosilicate glass burette with a cross section of 11-e*”. A column made of 2s&C-o-phen filled with gravity moves downward at 1tsQ/s. The flow rate in! I let it pass. PL in influent and effluent, Pd%I? h and Ru Each concentration was determined by direct current plasma spectrometry.

The results are presented in Table 3.4 as a function of the number of column volumes of solution passed through each ridge.

Table 3 CV Solution A concentration (g/e) Pt <0.7 Pd Rh2 <0.7 <0.02> 3.13 <0.6 <0.02 4.74 <0. s　 < 0.02 16.65 <O, 8 <O, 021g, 911 < 0.6 6.213 ＜ 0.8 　 　 　 　 　 0.01 6.520 < 0. 7 0.0B 5.325 < 0.8 < 0.03 5.63G ＜ 0.5 ＜ ＜ O, Q4 6.0 Influent 16.1 20.2 22.8 Table 4 CV　　　　　　　　　　　　　　　　B concentration (mg # Pt Pd Ru3 < 0.7 0.22 0.934 <0.4 0.19 5.65 0.5 0.13 8.77 < 0.9 0.04 8.013 < 0.6 0.04 g , 415 < 0.7 < 0.01 7. 92G < 0.8 < 0.04 8.4 25 　 　 　 　 　 　 ＜ 0.9 < 0.05 8.930 8.930 < 0.8 < 0.03 9.4 Inflow liquid 16.1 16.1 19.4 According to these results, pt from Rh and Ru solutions and 1,10-phenanthroline sorbed on Jl charcoal to remove Pd. It was found that using wo was effective.

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Claims (39)

[Claims] (1) Groups 5a, 6a, 7a, 8, and 1 of the periodic table are printed on the inner surface of the support. Transition metal ions of the group consisting of - or more ions of elements of group b and group 2b A heteropolycyclic compound component capable of forming a complex with a stable compound is included. (b) Presence of polycyclic compound component in sufficient amount to form a compound or complex with transition metal ion. It is characterized by an activated carbonaceous porous support having mutually communicating pores. A solution is passed through a composition containing a compound containing compounds of groups 5a, 6a, and 7a of the periodic table. consisting of one or more ions of elements of Group 8, Group 1b and Group 2b A method for removing one or more selected transition metal ions from a solution. (2) Claim 1, wherein the heteropolycyclic compound component has a bipyridyl structure. How to remove it. (3) Claim 1 in which the heteropolycyclic compound component has a phenanthroline structure. Removal method described in Section 1. (4) The removal method according to claim 1, wherein the solution is an aqueous solution. (5) Transition metal ions include iron, cobalt, nickel, and copper ions. Claim 1 contains one or more selected ions. removal method. (6) The solution contains more polyvalent metal ions than transition metal ions. A removal method according to claim 1. (7) Other polyvalent metal ions include titanium, zirconium, hafnium, and thorium. , lanthanum, aluminum, potassium, indium, scandium and yttrium Contains one or more ions selected from the group consisting of ions of 6. The removal method according to claim 6. (8) A patent claim in which the concentration of other metal ions in the solution is at least about 10 g/l The removal method described in item 7. (9) A patent claim in which other metal ions include zirconium and hafnium The removal method described in Scope Item 7. (10) The removal method according to claim 1, wherein the porous support is charcoal. . (11) The heteropolycyclic compound component is attached to the porous support by sorption from the solution. The removal method according to claim 1, which comprises: (12) The heteropolycyclic compound component is formed between the porous support and the heteropolycyclic compound component. Claim 1, which is attached to a porous support without covalent bonding. How to remove it. (13) After passing the solution through the composition, the concentration of transition metal ions in the solution is higher than that of other metals. Claim 6 wherein the concentration of ions is less than about 1 part per million. Removal method described in section. (14) On the inner surface of the support body, the periodic table's 5a bales, 6a groups, 7a groups, 8 groups, transition metal ions of the group consisting of one or more ions of elements of groups 1b and 2b; Heteropolycyclic compounds capable of forming stable compounds and complexes with at least one of to make the heteropolycyclic compound components visible among the transition metal ion groups in the column effluent. characterized in that they are present in an amount effective to cause severe separation, and are in communication with each other. passing the solution through a composition comprising an activated carbonaceous porous substrate having pores; , Groups 5a, 6a, 7a, 8, 1b and 2b of the periodic table one or more transitions selected from the group consisting of one or more ions of the element; A method for removing transferred metal ions from solution. (15) Claim 14, wherein the heteropolycyclic compound component has a bipyridyl structure. Removal method described in section. (16) Claims in which the heteropolycyclic compound component has a phenanthroline structure The removal method described in paragraph 14. (17) The removal method according to claim 14, wherein the solution is an aqueous solution. (18) Transition metal ions include rhenium, ruthenium, rhodium, palladium, and one or more ions selected from the group consisting of smium, iridium and platinum ions; The removal method according to claim 14, which contains the above ions. (19) Elimination according to claim 14, wherein the porous support is charcoal. Law. (20) The heteropolycyclic compound component is attached to the porous support by sorption from the solution. 15. The removal method according to claim 14. (21) The pH value of the aqueous solution is about 4 or less. The removal method according to any one of Item 17. (22) Claim 4 or 17, wherein the pH value of the aqueous solution is about 2 or less. The removal method described in any one of paragraphs. (23) One or more transition metal ions selected from the ion group on the composition is less than the concentration of transition metal ions in the solution before the solution is contacted with the composition. Claims 4 or 14 which are higher by a multiple of at least 10 times or more or the removal method described in item 1. (24) The method of claim 23, wherein the multiple is at least about 50. (25) Claim 2 in which the transition metal ion includes a radioactive ion. Removal method described in Section 3. (26) Transition metal ions include rhenium, ruthenium, rhodium, palladium, and one or more ions selected from the group consisting of smium, iridium and platinum ions; The removal method according to claim 23, which contains the above ions. (27) The composition of the patent claim contains charcoal as a porous support. Removal method according to scope item 23. (28) Exception as described in claim 27, which is obtained by subjecting the porous support to subsequent ashing treatment. Leaving the law. (29) The composition is then eluted and transition metal ions are provided again in the solution. A removal method according to claim 23. (30) comprising an activated carbonaceous porous substrate having interconnected pores; A composition comprising a heteropolycyclic compound component contained in the inner surface of a support. (31) The concentration of the heteropolycyclic compound component is at least about 0.1 dry weight relative to the support. % of the composition of claim 30. (32) Claims in which the heteropolycyclic compound component has a bipyridyl structure The composition according to item 30. (33) A patent claim in which the heteropolycyclic compound component has a phenanthroline structure The composition according to item 30. (34) The composition according to claim 30, wherein the porous support is charcoal. thing. (35) comprising an activated carbonaceous porous substrate having interconnected pores; The inner surface of the support contains heteropolycyclic compound components and groups 5a, 6a, and 7 of the periodic table. consisting of one or more ions of elements of group a, group 8, group 1b and group 2b and one or more transition metal ions selected from the group consisting of: . (36) The concentration of the heteropolycyclic compound component is at least about 0.1 dry weight relative to the support. 36. The composition of claim 35 in %. (37) Claims in which the heteropolycyclic compound component has a bipyridyl structure Composition according to paragraph 35. (38) A patent claim in which the heteropolycyclic compound component has a phenanthroline structure The composition according to item 35. (39) The composition according to claim 35, wherein the porous support is charcoal. thing.